Azo-dyestuffs insoluble in water



3,037,974 AZO-DYESTUFFS INSOLUBLE IN WATER Herbert Kracker, Fritz Bauer, and Werner Kirst, Offenbach (Main), Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed Feb. 17, 1959, Ser. No. 793,698 Claims priority, application Germany Feb. 21, 1958 1 Claim. (Cl. 260-160) The present invention relates to new azo-dyestutfs insoluble in water and to a process for preparing the same; more particularly it relates to dyestufls corresponding to the following general formula wherein the benzene nuclei a and b may contain as substituents halogen atoms, alkyl, alkoxy or nitro groups and R represents an alkyl or carboxylic acid ester group.

In US. patent application Serial No. 780,249, now abandoned, filed December 15, 1958 in the name of Herbert Kracker, Fritz Bauer, Werner Kirst and Walter Staab, there is disclosed a process for the manufacture of azo-dyestuffs insoluble in water, wherein the diazonium compound from a meta-amine-azo compound of the general formula wherein the benzene nuclei a and b may be substituted by halogen atoms, alkyl, alkoxy or nitro groups, is coupled in substance, on the fiber or on another substratum with an arylamide of an aromatic or heterocyclic orthohydroxy-carboxylic acid or acyl-acetic acid free from groups imparting solubility in water.

These dyestuffs yield on fibers of aromatic polyesters particularly of polyethylene-terephthalates, valuable dye ings which are distinguished by good properties of fastness. The dyestufls can also be produced on other synthetic fibers, such as acetyl-cellulose, triacetyl-cellulose or polyamide fibers, or on vegetable and also on animal fibers. Also on these fibers valuable dyeings are obtained.

The dyestuffs can also be prepared in substance or on a substratum, and they may be used for coloring plastic masses of high molecular weight or for the preparation of color lakes. Furthermore, they may be used for the manufacture of colored films by incorporating them in masses of cellulose esters or ethers, or they may be applied to textiles by the pigment printing process.

Now we have found that valuable azo-dyestufis insoluble in water of similar good properties of fastness are obtained by using as coupling components instead of the said arylamides of aromatic or heterocyclic ortho-hyice droxy-carboxylic acids or acylacetic acids l-aryl-S-pyrazclones of the general formula a ryl wherein R represents an alkyl or carboxylic acid ester group. As coupling components there may be used, for instance, the following compounds: l-phenylor l-naphthyl-3-alkyl-5-pyrazolones or l-phenylor l-naphthyl-S- pyrazolone-3-car-boxylic acid alkyl esters containing further substituents in the phenyl or naphthyl radical, such as, for instance, one or more halogen atoms, alkyl, alkoxy or nitro groups. R may represent, for instance, a methyl group or a carbomethoxy radical.

The new dyestuffs so obtained yield on fibers of aromatic polyesters, particularly polyethylene-terephthalates, valuable yellow dyeings of good properties of fastness. The dyestuifs can also be produced on other synthetic fibers such as acetyl-cellulose, triacetyl-cellulose or poly amide fibers and also on vegetable or animal fibers. Also on these fibers valuable dyeings are obtained.

The dyestuffs can also be produced in substance or on a substratum or they can be used for coloring plastic masses of high molecular weight or for the preparation Example 1 1 kilogram of polyethylene-glyool-terephthalate silk is treated in a closed apparatus for 90 minutes at 120 C. in the following bath: I

i 60 grams of 1-(2',5'-dichlorophenyl)3-methyl-5-pyrazolone and 6.2 grams of 3-amino-4-methoxy-l.l-azobenzene are dissolved at 90 C. in a mixture of 1 120 cc. of diacetone alcohol,

30 cc. of the sodium salt of sulfonated castor oil of 50% strength and 22.7 cc. of sodium hydroxide solution of 38 B.

the addition of 61 cc. of methoxybutylacetate, the solution is stirred into 20 liters of Water at 90-95 C.

The materials is then rinsed and diazotized with 36 grams of sodium nitrite and 100 grams of sulfuric acid of 96% strength in 20 liters of water by introducing the material, heating the bath to C. and treating the material for 30 minutes at this temperature. The material is then after-treated for 15 minutes at 80 C. in a solution containing per liter of water 4 cc. of sodium hydroxide solution of 38 B. and 2 grams of sodium dithionite to which a washing agent has been added, rinsed again and dried.

A yellow dyeing of very good properties of fastness is obtained.

After Example 2 1 kilogram of combed material of polyethylene-glycolterephthalate is treated for minutes at -100 C. in the following bath:

22.4 grams of 1-(2'-naphthyl)-3-methyl-5 pyrazolone are dissolved in 9 cc. of sodium hydroxide solution of 38 B. and hot water. The solution is then made up to 20 liters with hot water at 90 C. To this bath are added 6.25 grams of 3-amino-4-methoXy- 1,-l'-azobenzene,

40 grams of tetrahydronaphthalene previously dissolved in a hot mixture of 2.5 grams of a dispersing agent of the type of an alkylarylsulfonate, 2.5 grams of diglycol, 10 grams of butyl alcohol and 25 grams 'of methoxybutyla'cet-ate.

The material is then rinsed hot and cold anddiazotized with 50 grams of sodium nitrite and 160 grams of sulfuric acid of 96% strength in 20 liters oiwater by introducing the material, heating the bath to 85 C. and treating the material for about 30 minutes at this temperature. The material is then rinsed, after-treated for 15 minutes at 80 C. in a solution containing pe liter of'water 4 cc. of sodium hydroxide solution of 38 B. and 2 grams of sodium 'dithionite to which a washing agent has been added, rinsed again'and dried. L

A yellow dyeing of very good properties of fastness is obtained. a a

' Example 3 Cotton fabric is padded on the foulard at 95-100 C. with the following solution, squeezed out to 100% and dried: 1 a a 11.4 grams of 1-(2-naphthyl)-3 rnethyl-5-pyrazolone are dissolved with 30 cent the sodium salt of sulfonated castor oil of 50% strength and 12 cc. of sodium hydroxide solution of.38 B. and the -solution is made up to 1 liter with water.

Example 4 1 kilogram of acetate rayon is treated tor 90 minutes at 75-80 C. in the following bath:

7.6 grams of l-phenyl--pyranolone-3carbonylic acid methylester and 2 grams of 3-amino-4'-methoxy-l,l-azobenzene are dissolved in a hot mixture of 20 00. of diacetone alcohol,

10 cc. of the sodium salt of sulfonated castor oil of 50% streng h and r 3.5 cc. of sodium hydroxide solution of 38 B. After the addition of V 3 grams of methoxybutylacetate, the solution is made up to 3 liters with water at 70 C.

a The material is then rinsed and diazotized for 45 minutes at 25 C. with 6 grams of sodium nitrite and grams of sulfuricacid of 96% strength in 3 liters of water,

rinsed, soaped for lS minutes at 79 C. with a solution containing per liter of water l gram of a condensation product from an aminoalkylsulfonic acid and a fatty acid of high molecular weight and a small quantity of ammonia, rinsed again and dried; 1 v

A full yellow dyeing. of good properties of fastness is obtained. 7

. 7 Example; 7 l kilogram" of acetate rayon is treated for 90 minutes at 708() C. inthe following bath: a

2 grams or 3-amino-4,6-dirnetl1yl-4'-methoxy-1,lf-aiobenzene are dissolved in 5 cc. ofdiacetonealcohol and I 2.5 cc. of the sodium salt of sulfonatedcastor oil of 50%:

strength and the solution is introduce'd into 3 liters of water at 70, C. containing 5 .cc. of the sodiumsalt of V sulfonatedcastor oil of 50% strength. V The material is then rinsed and diazotized for 30 min.-

- 4 utes at 25 C. with 5.4 grams of sodium nitrite and 15 grams of sulfuric acid of 96% strength in 3 liters of Water. The material is then rinsed and treated in a bath containing a solution of 10.4 grams of l'-phenyl-3-methyl-5- pyrazolone in 2.7 cc. of sodium hydroxide solution of 38 Be. made up to 3 liters with water, and also 3 grams of monosodiumphosphate, by introducing the material, slowly heating the bath to 60 C., and treating the material for 30 minutes at this temperature, his then rinsed and dried.

A clear yellow dyeing of good properties of fastness is obtained.

Example 6 25.7 grams of 3-.arnino-6,4-dimethoxy-l,l'-azobenzene are diazotized in the usual manner. The diazo solution so obtained is run, while stirring well, into a suspension obtained by dissolving 22.4 grams of 1-(2'-naphthy1)-3- methyl-S-pyrazolone in denatured alcohol and dilute sodium hydroxide solution, and reprecipitating the compound with acetic acid. When the coupling is complete, the dyestufi obtained is filtered off with suction, washed and dried. It is a yellow powder. The coupling can also be carried out the the presence of a substratum adapted for the preparation of color lakes.

The following table indicates a number of further components which can be used in this invention, and also the tints of the azo-dyestutfs produced from the components on the fiber, which likewise possess good properties of iastness.

Coupling Component Diazo Component Matagialdto be Tint 1-phenyl-3-methyl-& 3-amino 4'-methoxypolyethyleneyellow.

pyrazolone. l,1'-azobenzene glycolterephthar late fiber.

Do 3-amino-4ethoxyacetate rayon. Do.

4-methoxy-1,1'- azobenzene.

Do a-amino-trethoxydo golden 4-methoxy-1,lyelazobenzene. low.

Do 3-axuimr3,4'-dido yellow,

methoxy-1,1'-azobenzene.

1-phenyl5-pyrazo- -do -.do Do.

lone-3-carboxylic acid methyl ester.

Do 3-amino-4,6-dido Do.

methyl-a meth0xy-1,1-az0- benzene. 1 7

Do 3-amino-4,4-dime- -do Do.

thoxy-1,1-azobenzene.

Do 3-amino4-ethoxy- .-do D0.

4-methoxy-1,lazobenzene.

1(2'-methylphenyl)- 3-amino-4,6-dido Do.

3fmethyl-5-pyrazomethyl4-me lone. thoxy-l,1-azobenzene.

Do S-amtnoA-ethoxy- --do Do.

annethoxy-LV- azobenzene.

Do 3-amino-6-ethoxy-4- do.-. golden methoxy-LP- 7 yellow.

. azobenzene. 7

Do 3-amino-4,4- -d0 Do.

dimethoxy-l,1- azobenzene. I 7

Do 3-amino-3Q4Gd1- --doyellow methoxy-LY-azobenzene.

Do 3- amino4-meth0xY- 'polyethylene- Do.

1,1-azobenzene. glycolter- 'ephtholate fiber. 1-(4-methylphenyl)- do do Do. 3-methy1-5-pyragolone. I Do..--;. S-amjnoA-ethoxyA acetate rayon-- Do. methoxy-1,1-azobenzene. Do 3-an1ino-4,4-dido Do.

" methoxy-l,l-azobenzene.

D0 3-amino-4,6-did0 Do.

methyl-4-meth- 0xy-l,1-azobenzene.

. Do 3-amino-3',4'-dido Do.

methoxy-1,1- azobenzene.

Coupling Component Diazo Component Mategialdto be Tint 1-(2',-ehlorophenyl)- 3-amino-4-methoxypolyethylene- Do.

3-methyl-5-pyraz- 1,l-azobenr.ene. glycololone. terephthalate fiber. 1-(2,5-dichloro- 3-amino-1,1-azodo D0.

pheny1)-3-metl1y1- benzene. 5-pyrazolone. 1-(2-naphthyl)-3- 3-amino-4-ethoxyd D0.

methyl--pyraz- 1,1-azobenzene. olone. l-(3-nitropheny1)3- 3-simino-4-metl1oxydo Do.

methyl-fi-pyraz- 1,1-az0benzene. olone. 1-(2-naphthyl)-3- 3-amino-1,1-azodo Do.

methyl-s-pyrazbenzene. olone.

Do 3-amino-4,4-dido Do.

methoxy-l, 1-azobenzene.

Do 3-amino-4-methyldo Do.

4-methoxy-1, 1-azobenzene.

D0 3-amino-4-ethoxyacetate rayon reddish 4-methoxy-1, yellow. l-azobenzene.

Do 3-amino-3,4- d0 yellow.

dimethoxy-I, l-axobenzene.

We claim:

The Water-insoluble azo-dyestuff corresponding to the following formula:

References Cited in the file of this patent UNITED STATES PATENTS 

